Process for depositing finely dispersed organic-inorganic films and articles made therefrom

ABSTRACT

A single hybrid organic-inorganic film. The film includes both an organic component, and an inorganic component. The organic component and inorganic component are well interspersed within the film. The film may be incorporated into a multilayer structure including a substrate. A method of forming a hybrid organic-inorganic film. The method includes generating a plasma stream with an expanding thermal plasma generator. The method also includes providing a first reactant and at least one second reactant into the plasma stream extending to a substrate, and forming the hybrid organic-inorganic film on the substrate.

BACKGROUND OF INVENTION

[0001] This invention is related generally to hybrid organic-inorganicfilms, products incorporating the hybrid films, and methods for makingthe films and products.

[0002] Products, such as windshields, that incorporate ultraviolet (UV)filters typically benefit from an abrasion resistant coating on the UVfilter to protect the filter and windshield from abrasion. The UVfiltering and abrasion resistance for such products are typicallyimplemented using an inorganic UV filter and a separate organic abrasionresistant coating. Unfortunately, this approach may suffer from longterm weathering failures due to strain occurring at the interfacebetween the inorganic UV filter and the organic adjacent layers orsubstrate due to differences in stress, coefficient of thermalexpansion, hardness and modulus.

[0003] In many coating applications where UV filters are coated, thesubstrate material is a polymer which is typically a material with asubstantially lower refractive index (RI) than that of the film orcoating used for the UV filter. In this case, interference patterns dueto the mismatch in refractive index (RI) between the low RI substrateand the high RI UV filter can be a serious problem, especially in 3Dapplications.

SUMMARY OF INVENTION

[0004] In accordance with one aspect of the present invention, there isprovided a single hybrid organic-inorganic film. The film comprises anorganic component and an inorganic component, wherein the organiccomponent and inorganic component are well interspersed within the film.

[0005] In accordance with another aspect of the present invention, thereis provided a multilayer structure. The multilayer structure comprises asubstrate and a hybrid organic-inorganic film. The hybridorganic-inorganic film comprises an organic component and an inorganiccomponent, wherein the organic component and inorganic component arewell interspersed within the film.

[0006] In accordance with another aspect of the present invention, thereis provided a method of forming a hybrid organic-inorganic film. Themethod comprises: generating a plasma; providing a first reactant and atleast one second reactant into the plasma extending to a substrate; andforming the hybrid organic-inorganic film on the substrate.

BRIEF DESCRIPTION OF DRAWINGS

[0007]FIG. 1 is a side cross sectional view of a substrate coated with ahybrid organic-inorganic layer according to an exemplary embodiment ofthe invention.

[0008]FIG. 2 is a side cross sectional view of an apparatus used tomanufacture the substrate coated with a hybrid organic-inorganic layeraccording to an exemplary embodiment of the invention.

[0009]FIG. 3 is a graph illustration of the behavior of the UVabsorbency and the index of refraction of the hybrid organic-inorganiclayer as a function of the volume % of the D4 organic component.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Structure with Hybrid Organic-Inorganic Coating

[0011] The preferred embodiments of the invention provide a process thatproduces a hybrid organic-inorganic film or layer of materials that aremixed as phases or components to provide properties that are nototherwise attainable. The phases are well interspersed. For example, themethod provides a single coating for a windshield glazing, or otherproduct glazing, that provides both abrasion resistance and UVprotection.

[0012] Preferably separate layers are utilized for the abrasionresistance and UV protection functions. For the UV functional layer,some of the organic phase is mixed into the inorganic layers and therebyreduce the stress in the inorganic coating and thereby reduce the strainat the interface between these layers. The hybrid coating also allowsfor the adjustment of refractive index, which allows the interferencepatterns in the final product to be reduced (the interference patternsare caused by refractive index differences between substrate andcoating).

[0013]FIG. 1 illustrates a structure 10 incorporating a hybridorganic-inorganic layer according to one embodiment of the invention.The structure includes a substrate 12 and a hybrid organic-inorganiclayer (or film) 14 disposed over the substrate. In this application,“layer” and “film” and “coating” are used interchangeably. The structure10 may optionally include an interlayer 16 disposed between thesubstrate 12 and the hybrid organic-inorganic layer 14, depending uponthe application. The interlayer 16 may function as an adhesion layerbetween the substrate 12 and the hybrid organic-inorganic layer 14 topromote adhesion between these layers, or may function to reduce stressbetween the substrate 12 and overlying layers, including the hybridorganic-inorganic layer 14 or may shield the substrate fromphoto-oxidation enhanced by titanium oxide which is known to be aphoto-oxidative catalyst. The interlayer 16 may comprise sublayers,where one sublayer functions to reduce stress between the substrate 12and the hybrid organic-inorganic layer 14, and the other sublayerfunctions to promote adhesion between the substrate 12 and the hybridorganic-inorganic layer 14. The structure 10 may also optionally includean abrasion resistant layer 18 on the hybrid organic-inorganic layer 14to protect the hybrid organic-inorganic layer 14 from abrasion.Alternatively, the hybrid organic-inorganic layer 14 may have abrasionresistant properties and the separate abrasion resistant layer 18 may beomitted. Other coatings, with functions such as IR reflecting,antireflecting, moisture barrier, electrically conductive, conductingoxide layers, and the like may be disposed between the hybridorganic-inorganic layer 14 and the interlayer 16 or abrasion resistantlayer 18, or on top of the abrasion resistant layer 18.

[0014] The substrate 12 may comprise, for example, a polymer resin. Forexample, the substrate may comprise a polycarbonate. Polycarbonatessuitable for forming the substrate are well-known in the art.

[0015] Aromatic carbonate polymers may be prepared by methods well knownin the art as described, for example, in U.S. Pat. Nos. 3,161,615;3,220,973; 3,312,659; 3,312,660; 3,313,777; 3,666,614; 3,989,672;4,200,681; 4,842,941; and 4,210,699, all of which are incorporatedherein by reference.

[0016] The substrate may also comprise a polyestercarbonate which can beprepared by reacting a carbonate precursor, a dihydric phenol, and adicarboxylic acid or ester forming derivative thereof.Polyestercarbonates are described, for example, in U.S. Pat. Nos.4,454,275; 5,510,448; 4,194,038; and 5,463,013, all of which areincorporated herein by reference.

[0017] The substrate may also comprise a thermoplastic or thermosetmaterial. Examples of suitable thermoplastic materials includepolyethylene, polypropylene, polystyrene, polyvinylacetate,polyvinylalcohol, polyvinylacetal, polymethacrylate ester, polyacrylicacids, polyether, polyester, polycarbonate, cellulous resin,polyacrylonitrile, polyamide, polyimide, polyvinylchloride, fluorinecontaining resins and polysulfone. Examples of suitable thermosetmaterials include epoxy and urea melamine.

[0018] Acrylic polymers, also well known in the art, are anothermaterial from which the substrate may be formed. Acrylic polymers can beprepared from monomers such as methyl acrylate, acrylic acid,methacrylic acid, methyl methacrylate, butyl methacrylate, cyclohexylmethacrylate, and the like. Substituted acrylates and methacrylates,such as hydroxyethyl acrylate, hydroxybutyl acrylate,2-ethylhexylacrylate, and n-butylacrylate may also be used.

[0019] Polyesters can also be used to form the substrate. Polyesters arewell-known in the art, and may be prepared by the polyesterification oforganic polycarboxylic acids (e.g., phthalic acid, hexahydrophthalicacid, adipic acid, maleic acid, terphthalic acid, isophthalic acid,sebacic acid, dodecanedioic acid, and the like) or their anhydrides withorganic polyols containing primary or secondary hydroxyl groups (e.g.,ethylene glycol, butylene glycol, neopentyl glycol, andcyclohexanedimethanol).

[0020] Polyurethanes are another class of materials which can be used toform the substrate. Polyurethanes are well-known in the art, and areprepared by the reaction of a polyisocyanate and a polyol. Examples ofuseful polyisocyanates include hexamethylene diisocyanate, toluenediisocyanate, MDI, isophorone diisocyanate, and biurets andtriisocyanurates of these diisocyanates. Examples of useful polyolsinclude low molecular weight aliphatic polyols, polyester polyols,polyether polyols, fatty alcohols, and the like.

[0021] Examples of other materials from which the substrate may beformed include acrylonitrile-butadiene-styrene, glass, VALOX®.(polybutylenephthalate, available from General Electric Co.), XENOY® (ablend of LEXAN® and VALOX®, available from General Electric Co.), andthe like. Typically, the substrate comprises a clear polymeric material,such as PC, PPC, PES, PEI or acrylic.

[0022] The substrate can be formed in a conventional manner, for exampleby injection molding, extrusion, cold forming, vacuum forming, blowmolding, compression molding, transfer molding, thermal forming, and thelike. The article or product formed may be in any shape and need not bea finished article of commerce, that is, it may be sheet material orfilm which would be cut or sized or mechanically shaped into a finishedarticle. The substrate may be transparent or not transparent. Thesubstrate may be rigid or flexible.

[0023] The substrate may be, for example, a vehicle window, such as acar, truck, motorcycle, tractor, boat or air plane window. The substratemay also comprise an eye glass lens, an optical stack, a display screen,such as a television screen, LCD screen, computer monitor screen, aplasma display screen or a glare guard for a computer monitor.

[0024] The hybrid organic-inorganic layer or film 14 comprises both anorganic component (or phase) and an inorganic component (or phase). Theorganic component and the inorganic component are interspersed withinthe single layer or film.

[0025] The hybrid organic-inorganic layer 14 may be formed by a varietyof plasma enhance chemical vapor deposition (PECVD) techniques known inthe art, and is preferably formed by an Expanding Thermal Plasma process(ETP), as discussed in more detail below. ETP processes, such as arcplasma deposition, and systems performing ETP, are generally known, andare described in U.S. Pat. No. 6,420,032, for example, which is hereinincorporated by reference in its entirety. The hybrid organic-inorganiclayer 14 may have a property associated with the inorganic component ofthe layer 14, such as UV absorption properties, and additionallyproperties associated with the organic component of the layer, such asUV absorbance, abrasion resistance, stress relief, and lower RI, forexample. The hybrid organic-inorganic layer 14 may also have propertiesthat are not associated with either of the components, but only with thecombination of components. These properties are beneficially combined ina single layer, i.e., the hybrid organic-inorganic layer 14.

[0026] The interlayer 16, if implemented, may function to relieve stressbetween the substrate 12 and the overlying layers. Stress may occur, forexample, due to different coefficients of thermal expansion, differentductility, and different elastic moduli between the substrate 12 and theoverlying layers. Preferably, the interlayer 16 comprises a materialwhich has a value of coefficient of thermal expansion, ductility, andelastic modulus which is between the corresponding values of thesubstrate and the overlying layers. Preferably the interlayer 16 ischemically resistant to photo induced oxidation by titanium oxidecoating. One example of a suitable interlayer material is a plasmapolymerized organosilicon, as described in the application Ser. No.09/271,654, entitled “Multilayer Article and Method of Making by ArcPlasma Deposition”, which is herein incorporated by reference in itsentirety. Optionally the interlayer 16 may be omitted and the hybridorganic-inorganic layer 14 layer itself may be of a composition torelieve stress between the substrate and itself and the overlyinglayers. In this regard, the hybrid organic-inorganic layer 14 may havesufficient organic material (or inorganic material for substrates with asimilar coefficient of thermal expansion to the inorganic material), forexample, to reduce stress. The hybrid organic-inorganic layer 14 layermay be deposited as a single layer or multiple layers sufficiently thickto achieve the desired properties. If more than one layer is utilized,they may all have the same composition or may vary to achieve varyingdegrees of properties for example UV filtering and/or abrasionresistance.

[0027] The abrasion resistant layer 18, if implemented, prevents thehybrid organic-inorganic layer 14 from being scratched during use. Theabrasion resistant layer 18 may comprise any scratch or abrasionresistant and UV stable material. The abrasion resistant layer 18 maycomprise, for example, a plasma polymerized organosilicon material, asdescribed in U.S. Ser. No. 09/271,654. The organosilicon material maycomprise, for example, octamethylcyclotetrasiloxane (D4),tetramethyldisiloxane (TMDSO), hexamethyldisiloxane (HMDSO), or otherorganosilicon, as described in the above application. The organosiliconmonomers are oxidized, decomposed, and polymerized in an arc plasmadeposition apparatus, to form an abrasion resistant layer whichcomprises an oxidized D4, TMDSO, or HMDSO layer, for example. Such anabrasion resistant layer may be referred to as a SiO_(x) layer. However,the SiO_(x) layer may also contain hydrogen and carbon atoms in whichcase it is generally referred to as SiO_(x)C_(y)H_(z). Other examples ofcompounds and materials suitable as the abrasion-resistant materialinclude silicon dioxide and aluminum oxide, for example. Preferably,however, the abrasion resistant layer 18 is omitted and the hybridorganic-inorganic layer 14 itself has good abrasion-resistantproperties.

[0028] Deposition System

[0029] The system for forming the hybrid organic-inorganic layer 14 ispreferably an ETP system such as described in U.S. Pat. No. 6,420,032.FIG. 2 illustrates an example of an appropriate system 100 for forming ahybrid organic-inorganic layer 14 according to embodiments of theinvention. The system of FIG. 2 is similar to the system of FIG. 4 ofU.S. Pat. No. 6,420,032. Other appropriate ETP systems are disclosed forexample in U.S. Pat. No. 6,397,776, entitled “APPARATUS FOR LARGE AREACHEMICAL VAPOR DEPOSITION USING MULTIPLE EXPANDING THERMAL PLASMAGENERATORS”, and U.S. patent application Ser. Nos. 09/683,148,09/683,149 and 10/064,888, all of which are hereby incorporated byreference in their entirety. These latter disclosures illustratefeatures such as multiple injection rings, one ring around several arcs,and/or an adjustable cathode to anode distance, which may be preferablein some applications.

[0030] The system 100 comprises a plasma generation chamber 110 and adeposition chamber 111. The deposition chamber 111 contains a substrate120 mounted on a temperature controlled support 122. The substrate 120may be a transparent glass or polymeric substrate 12, for example,coated with the interlayer 16, if implemented, as shown in FIG. 1. Thedeposition chamber 111 also contains a door (not shown) for loading andunloading the substrate 120 and an outlet 123 for connecting to a pump.The support 122 may be positioned at any position in volume 121 ofdeposition chamber 111. The substrate 120 may be positioned 10 to 50 cm,for example, and typically about 25.5 cm, from the anode 119 of theplasma generator.

[0031] The deposition chamber 111 also optionally comprises aretractable shutter 124. The shutter 124 may be positioned, for example,by a handle 125 or by a computer controlled positioning mechanism. Theshutter 124 may also contain a circular aperture to control the diameterof the plasma that emanates from the plasma generation chamber 110towards the substrate 120. The deposition chamber 111 may alsooptionally comprise magnets or magnetic field generating coils (notshown) adjacent to chamber walls to direct the flow of the plasma.

[0032] The deposition chamber 111 may also contain an optional nozzle118. The nozzle 118 provides improved control of the injection,ionization and reaction of the reactants to be deposited on thesubstrate 120. The nozzle 118 provides for the deposition of a materialsuch as the hybrid organic-inorganic layer on the substrate 120 andminimizes or even prevents formation of powdery reactant deposits on thesubstrate 120. Preferably, the nozzle 118, if employed, has a conicalshape with a divergent angle of about 40 degrees and a length of about10 to 80 cm, preferably about 16 cm. However, the nozzle 118 mayalternatively have a variable cross section, such as such asconical-cylindrical-conical or conical-cylindrical. Furthermore, thenozzle 118 may have a divergent angle other than 40 degrees and a lengthother than 16 cm. The nozzle may also be omitted entirely.

[0033] The deposition chamber 111 also contains at least one reactantsupply line. For example, the deposition chamber 111 may contain a firstreactant supply line 112, a second reactant supply line 114, and a thirdreactant supply line 116 to deposit the hybrid organic-inorganic layeron the substrate 120. The supply lines 112, 114 and 116 preferablycommunicate with the nozzle 118 and supply reactants into the plasmaflowing through the nozzle. The deposition chamber 111 also generallycontains vacuum pumps (not shown) for evacuating the chamber 111.

[0034] The plasma generation chamber 110 contains at least one cathode113, a plasma gas supply line 117 and an anode 119. The plasmageneration chamber 110 typically comprises three cathodes 113. Thecathodes 113 may comprise, for example, tungsten or thorium dopedtungsten tips.

[0035] The plasma generation chamber 110 generally includes at least oneplasma gas supply line 117. The plasma generation chamber 110 may alsocontain a purging gas supply line adjacent to the carrier gas supplyline 117 to supply a purging gas to chambers 110 and 111 prior tosupplying the plasma gas.

[0036] To form a plasma in the plasma generation chamber 110, a plasmagas is supplied through plasma gas supply line 117. The plasma gas maysuitably comprise a noble gas, such as argon or helium, or a reactivegas, such as nitrogen, ammonia, carbon dioxide or hydrogen or anymixture thereof. If there is more than one plasma gas, then the pluralgasses may be supplied through plural supply lines, if desired.Preferably, for the hybrid organic-inorganic layer deposition, theplasma gas comprises argon. The plasma gas in plasma generation chamber110 is maintained at a higher pressure than the pressure in thedeposition chamber 111, which is continuously evacuated by a pump. Anarc voltage is then applied between the cathode(s) 113 and the anode 119to generate a plasma in the plasma generation chamber 110. The plasmathen extends through the aperture of the anode 119 into the depositionchamber 111 due to the pressure difference between chambers 110 and 111.The reactants are supplied into the plasma through supply lines 112, 114and 116.

[0037] Methods of Forming the Hybrid Organic-Inorganic Layer

[0038] A method of forming hybrid organic-inorganic layers according toan embodiment of the present invention is now described. The hybridorganic-inorganic layers were formed by ETP deposition ontopolycarbonate substrates. The hybrid organic-inorganic layers comprisean organic component formed from octamethylcyclotetrasiloxane (D4) andan inorganic component of TiO₂. The organic component formed from D4 isreferred to in this application as the D4 organic component. The D4organic component may be SiOx, but may also contain hydrogen and carbonatoms in which case it is generally referred to as SiO_(x)C_(y)H_(z).

[0039] An Ar expanding thermal plasma (ETP) was generated. A first andat least one second reactant are then supplied to the plasma via supplylines. The first reactant as the source of titanium may be any volatileoxidizable Ti containing precursor. Preferably Ti-alkoxides (e.g.,isopropoxide) may be used. The at least one second reactant may includewater or oxygen or other organotitanate. Preferably the first reactantcomprises TiCl₄ and the at least second reactant comprises water vaporand D4. The first and at least one second reactants react and form ahybrid organic-inorganic film on the substrate. Specifically, the Arexpanding thermal plasma (ETP) was used to simultaneously plasma oxidizeTiCl₄ to form a titanium oxide, such as TiO₂ or non-stoichiometricTiO_(x), inorganic component and plasma polymerize and oxidizeoctamethylcyclotetrasiloxane (D4) to form the D4 organic component. Thewater was fed to the ETP as an oxidant.

[0040] D4, TiCl₄ and water vapor were supplied as reactant gases asfollows. A series of samples were formed with hybrid organic-inorganiclayers or coatings having a progressively increasing volume percent ofD4 organic component in the hybrid coating. The hybrid organic-inorganiccoating had progressively a volume percent ranging from 25-75% D4organic component. The increasing amount of D4 organic component wasimplemented by appropriately adjusting the flow rates of D4 and TiCl₄,with an increase in D4 flow rate producing a greater volume percent ofD4 organic component. Table 1 lists the deposition parameters for thehybrid organic-inorganic layer of TiO₂ and D4 organic components. TABLE1 TiCl₄ D4 Ar H₂O Thickness D4 Stress RI at Ex. lpm lpm lpm lpm A (nm)Vol. % (psi) 580 nm 1 0.2 0 3 0.8 1.1 230 0 95000 2.3 2 0.2 0 1.22 3 0.20.8 1.23 4 0.2 .01 3 0.8 1.1 316 25 2.08 5 0.2 0.016 1.19 6 0.2 0.0250.91 7 0.2 .03 3 0.8 0.79 590 75 1.66 8 0.6 0 5 2.4 1.53 360 0 44819 2.39 0.6 .03 5 2.4 1.19 925 43 −4176 1.93 10 0.6 .06 5 2.4 1.12 1002 58−5198 1.81 11 0.6 .10 5 2.4 0.89 1337 69 −3465 1.71 12 1 0 5 4 2.3 533 029326 2.3 13 1 .03 5 4 1.84 1358 34  3233 2.01 14 1 .06 5 4 1.82 1342 48−1376 1.89 15 1 .10 4 1.68 1547 54 −2136 1.81

[0041] All examples in Table 1 were performed at a current of 80 Ampsand a voltage of 30 V. All the examples in Table 1 were coated at 45 mT(milliTorr), preheating the substrate to ˜120° C., at a scan rate of 2.3cm/s for a coating time of 7 seconds. The volume % of the D4 organiccomponent in the coating was determined from ellipsometry and is listedin Table 1. The absorbency (A) was measured at 330 nm. The stress wascalculated from the bowing of a Si wafer using an Ionic Systems stressgauge SGII. The Argon (Ar), water (H₂O), TiCl₄, and D4 flow rates arelisted in table 1. The stress (in psi), refractive index, film thicknessand absorbency are also listed.

[0042] The coatings from table 1 were well adhered and clear. Theas-deposited coatings were subjected to a water immersion test asfollows. The water immersion test consisted of submerging the hybridorganic-inorganic coating, formed on the substrate for 3 days indistilled water at 65° C. All of the hybrid organic-inorganic coatingslisted in Table 1 passed the water immersion test showing no loss ofabsorbency after immersion for 3 days in distilled water at 65° C.

[0043] A significant property of the progressive coatings listed inTable 1 is that the behavior of the refractive index (RI) and extinctioncoefficient (measured as the absorbency at 330 nm) as a function of theD4 organic component volume percent was not the same. The RI increasedlinearly with the volume percent of TiO₂, and essentially followed thefollowing formula: RI=(RI _(D4)×(volume percent D4 organiccomponent))+(RI_(TiO2)×(volume percent TiO₂)), where RI_(D4) is the RIof a pure D4 organic component film, and RI_(TiO2) is the RI of a pureTiO₂ film.

[0044] On the other hand, the absorbency of the hybrid organic-inorganiccoatings was equal to that of a pure TiO₂ film up to about 30 volume %D4 organic component. Even at about 75% D4, the absorbency of the hybridcoating was ⅔ that of a pure TiO₂ film. Furthermore, as shown in Table 1the stress (the intrinsic stress) of the coating can be tailored fromhighly tensile to compressive allowing matching of layers in amulti-layer stack. The zero stress state occurs at ˜35% organic coating.

[0045] Because the extinction coefficient remains that of a pure TiO₂film up to about 25 volume % D4 organic component, and does not drop offsignificantly up to about 75% D4 organic component, a hybrid coating canbe made which is a significantly more ductile coating than a pure TiO₂film and does not have a significant interference fringes problem due toa large mismatch of the coating RI with the polycarbonate substrate. Atthe same time the hybrid coating still provides substantial filtering ofUV.

[0046] Thus, the series of samples with progressively increasing volume% of organic component provides an example of a film with a propertyassociated with one of the organic component and inorganic component,where that property remains substantially constant over a range ofvolume percents of respective organic and inorganic components. In thiscase the property is the UV absorbency associated with the inorganiccomponent. The stress was non-linear with the volume %.

[0047] The series of samples with progressively increasing volume % oforganic component also provides an example of a film with a propertyassociated with one of the organic component and inorganic component,where that property changes linearly with the volume percent of therespective organic and inorganic components over a range of volumepercents. In this case the property is the RI where the RI changeslinearly with the volume percent of the inorganic component over therange of volume percents.

[0048]FIG. 3 is a graph qualitatively illustrating the behavior of theUV absorbency and the index of refraction of the hybridorganic-inorganic layer as a function of the volume % of the D4 organiccomponent. As can be seen the index of refraction changes linearly withthe volume % of the D4 organic component, while the UV absorbencyremains relatively constant up to about 25% D4.

[0049] One advantage of using ETP is that deposition is extremely fastso phases or components do not have time to settle out and segregate asthey do in other film formation techniques, such as the sol-gelapproach. Thus, ETP allows for the intimate mixing of organic andinorganic phases interspersed in a single film. Because a hybrid filmcan be formed, properties otherwise unattainable can now be obtained.The above description describes a particular hybrid coating with TiO₂and D4 organic component components. However, other hybrid films orcoatings can be deposited using ETP.

[0050] While the invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope of the invention.Thus, the breadth and scope of the present invention should not belimited by any of the above-described exemplary embodiments, but shouldbe defined only in accordance with the following claims and theirequivalents.

1. A single hybrid organic-inorganic film comprising: an organiccomponent; and an inorganic component, wherein the organic component andinorganic component are well interspersed within the film.
 2. The filmof claim 1, wherein the organic component comprises anoctamethylcyclotetrasiloxane (D4) organic component and the inorganiccomponent comprises titanium oxide.
 3. The film of claim 1, wherein thefilm comprises between 10% and 90% organic component by volume.
 4. Thefilm of claim 1, wherein the organic component comprises an abrasionresistant material and the inorganic component comprises an ultraviolet(UV) filter material.
 5. The film of claim 4, wherein the film comprisesbetween 10% and 90% organic component by volume.
 6. The film of claim 1,wherein a first property is associated with the organic component and asecond property is associated with the inorganic component, and one ofthe first and second properties remains substantially constant over arange of volume percents of respective organic and inorganic components.7. The film of claim 6, wherein the second property is UV absorbency andthe UV absorbency remains substantially constant over the range ofvolume percents of the inorganic component.
 8. The film of claim 1,wherein a first property is associated with the organic component and asecond property is associated with the inorganic component, and one ofthe first and second properties changes linearly with the volume percentof the respective organic and inorganic components over a range ofvolume percents.
 9. The film of claim 8, wherein the first property isrefractive index (RI) and the RI changes linearly with the volumepercent of the inorganic component over the range of volume percents.10. The film of claim 8, wherein the first property is a stress of thefilm and the stress changes linearly with the volume percent of theinorganic component over the range of volume percents.
 11. A multilayerstructure comprising: a substrate; and a hybrid organic-inorganic film,the hybrid organic-inorganic film comprising: an organic component; andan inorganic component, wherein the organic component and inorganiccomponent are well interspersed within the film.
 12. The structure ofclaim 11, further comprising: an interlayer disposed between thesubstrate and the hybrid organic-inorganic film.
 13. The structure ofclaim 11, further comprising: an abrasion resistant layer disposed onthe hybrid organic-inorganic film.
 14. The structure of claim 11,further comprising: at least one of an IR reflecting layer, anantireflecting layer, a transparent conducting oxide layer, and amoisture barrier.
 15. The structure of claim 13, wherein the abrasionresistant layer comprises an octamethylcyclotetrasiloxane (D4) organiccomponent.
 16. The structure of claim 11, wherein the substratecomprises a polymer.
 17. The structure of claim 16, wherein thesubstrate comprises polycarbonate.
 18. The structure of claim 11,wherein the organic component comprises an octamethylcyclotetrasiloxane(D4) organic component and the inorganic component comprises titaniumoxide.
 19. The structure of claim 11, wherein the film comprises between10% and 90% organic component by volume.
 20. The structure of claim 11,wherein the organic component comprises an abrasion resistant material.21. The film of claim 11, wherein the inorganic component comprises anultraviolet (UV) filter material.
 22. A method of forming a hybridorganic-inorganic film, the method comprising: generating a plasma;providing a first reactant and at least one second reactant into theplasma extending to a substrate; and forming the hybridorganic-inorganic film on the substrate.
 23. The method of claim 22,wherein the generating a plasma comprises generating a plasma streamwith an expanding thermal plasma generator.
 24. The method of claim 23,wherein the first reactant comprises TiCl₄ and the at least one secondreactant comprises water vapor and octamethylcyclotetrasiloxane (D4).25. The method of claim 23, wherein the plasma comprises an Ar plasma.26. The method of claim 23, further comprising: supplying the firstreactant into the plasma at a rate of between 0.1 and 10 μm, and the atleast one second reactant into the plasma at a rate of 0.1 to 1 lpm. 27.The method of claim 26, further comprising: supplying the first reactantinto the plasma at a rate of between 0.2 and 2 lpm, and the at least onesecond reactant into the plasma at a rate of 0.01 to 0.2 lpm.
 28. Themethod of claim 23, wherein the hybrid organic-inorganic film comprises:an organic component; and an inorganic component, wherein the organiccomponent and inorganic component are well interspersed within the film.29. The method of claim 23, wherein the first reactant comprises a metalcontaining gas and the at least one second reactant comprisessiloxane/organosilicon.
 30. The method of claim 23, wherein the at leastone second reactant further comprises water.
 31. The method of claim 23,wherein the first reactant comprises a volatile titanium alkoxide ortitanium halide and the second reactant comprises at least one ofoctamethylcyclotetrasiloxane (D4), tetramethyldisiloxane (TMDSO), andhexamethyldisiloxane (HMDSO).
 32. The method of claim 28, wherein thefilm comprises between 10% and 90% organic component by volume.
 33. Themethod of claim 28, wherein the organic component comprises an abrasionresistant material and the inorganic component comprises an ultraviolet(UV) filter material.
 34. The method of claim 33, wherein the filmcomprises between 10% and 90% organic component by volume.
 35. Themethod of claim 28, wherein a first property is associated with theorganic component and a second property is associated with the inorganiccomponent, and one of the first and second properties remainssubstantially constant over a range of volume percents of respectiveorganic and inorganic components.
 36. The method of claim 35, whereinthe second property is UV absorbency and the UV absorbency remainssubstantially constant over the range of volume percents of theinorganic component.
 37. The method of claim 28, wherein a firstproperty is associated with the organic component and a second propertyis associated with the inorganic component, and one of the first andsecond properties changes linearly with the volume percent of therespective organic and inorganic components over a range of volumepercents.
 38. The method of claim 37, wherein the first property isrefractive index (RI) and the RI changes linearly with the volumepercent of the inorganic component over the range of volume percents.39. The method of claim 38, wherein the first property is a stress ofthe film and the stress changes linearly with the volume percent of theinorganic component over the range of volume percents.